Ultrafast rotation in an amphidynamic crystalline metal organic framework

Vogelsberg, Cortnie S.; Uribe-Romo, Fernando J.; Lipton, Andrew S.; Yang, Song; Houk, K. N.; Brown, Stuart; Garcia-Garibay, Miguel A.

doi:10.1073/pnas.1708817115

Title: Ultrafast rotation in an amphidynamic crystalline metal organic framework

Journal Article · Tue Dec 26 00:00:00 EST 2017 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1708817115· OSTI ID:1427926

Vogelsberg, Cortnie S. ^[1]; Uribe-Romo, Fernando J. ^[2];

^[3]; Yang, Song ^[1]; Houk, K. N. ^[1]; Brown, Stuart ^[1];

^[1]

Univ. of California, Los Angeles, CA (United States)
Univ. of Central Florida, Orlando, FL (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Amphidynamic crystals are an emergent class of condensed phase matter designed with a combination of lattice-forming elements linked to components that display engineered dynamics in the solid state. Here, we address the design of a crystalline array of molecular rotors with inertial diffusional rotation at the nanoscale, characterized by the absence of steric or electronic barriers. We solved this challenge with 1,4-bicyclo[2.2.2]octane dicarboxylic acid (BODCA)-MOF, a metal-organic framework (MOF) built with a high-symmetry bicyclo[2.2.2]octane dicarboxylate linker in a Zn₄O cubic lattice. Using spin-lattice relaxation ¹H solid-state NMR at 29.49 and 13.87 MHz in the temperature range of 2.3–80 K, we showed that internal rotation occurs in a potential with energy barriers of 0.185 kcal mol^-1. These results were confirmed with ²H solid-state NMR line-shape analysis and spin-lattice relaxation at 76.78 MHz obtained between 6 and 298 K, which, combined with molecular dynamics simulations, indicate that inertial diffusional rotation is characterized by a broad range of angular displacements with no residence time at any given site. Furthermore, the ambient temperature rotation of the bicyclo[2.2.2]octane (BCO) group in BODCA-MOF constitutes an example where engineered rotational dynamics in the solid state are as fast as they would be in a high-density gas or in a low-density liquid phase.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1427926

Report Number(s):: PNNL-SA-125469; 45292; KP1704020

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Vol. 114, Issue 52; ISSN 0027-8424

Publisher:: National Academy of Sciences, Washington, DC (United States)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 66 works

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References (23)

Rotation of a Bulky Triptycene in the Solid State: Toward Engineered Nanoscale Artificial Molecular Machines Jiang, Xing; Rodríguez-Molina, Braulio; Nazarian, Narega Journal of the American Chemical Society, Vol. 136, Issue 25 https://doi.org/10.1021/ja503467e	journal	June 2014
Dynamic Characterization of Crystalline Supramolecular Rotors Assembled through Halogen Bonding Catalano, Luca; Pérez-Estrada, Salvador; Terraneo, Giancarlo Journal of the American Chemical Society, Vol. 137, Issue 49 https://doi.org/10.1021/jacs.5b10776	journal	December 2015
Modular Chemistry: Secondary Building Units as a Basis for the Design of Highly Porous and Robust Metal−Organic Carboxylate Frameworks Eddaoudi, Mohamed; Moler, David B.; Li, Hailian Accounts of Chemical Research, Vol. 34, Issue 4, p. 319-330 https://doi.org/10.1021/ar000034b	journal	April 2001
Rotational jumps of the tyrosine side chain in crystalline enkephalin. Hydrogen-2 NMR line shapes for aromatic ring motions in solids Rice, David M.; Wittebort, Richard J.; Griffin, Robert G. Journal of the American Chemical Society, Vol. 103, Issue 26 https://doi.org/10.1021/ja00416a002	journal	December 1981
A General Theory of Magnetic Resonance Absorption Kubo, Ryogo; Tomita, Kazuhisa Journal of the Physical Society of Japan, Vol. 9, Issue 6 https://doi.org/10.1143/JPSJ.9.888	journal	November 1954
Molecular dynamics of solid polymers as revealed by deuteron NMR Spiess, H. W. Colloid & Polymer Science, Vol. 261, Issue 3 https://doi.org/10.1007/BF01469664	journal	March 1983
Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage Eddaoudi, Mohamed; Kim, Jaheon; Rosi, Nathaniel Science, Vol. 295, Issue 5554, p. 469-472 https://doi.org/10.1126/science.1067208	journal	January 2002
Molecular Rotors and Motors: Recent Advances and Future Challenges Michl, Josef; Sykes, E. Charles H. ACS Nano, Vol. 3, Issue 5 https://doi.org/10.1021/nn900411n	journal	April 2009
Surface-mounted altitudinal molecular rotors in alternating electric field: Single-molecule parametric oscillator molecular dynamics Horinek, D.; Michl, J. Proceedings of the National Academy of Sciences, Vol. 102, Issue 40 https://doi.org/10.1073/pnas.0506183102	journal	September 2005
A Simple Modification of the Wolff-Kishner Reduction Huang-Minlon, [not available] Journal of the American Chemical Society, Vol. 68, Issue 12 https://doi.org/10.1021/ja01216a013	journal	December 1946
Zur Konformation des Bicyclo[2.2.2]octan-Systems Ermer, O.; Dunitz, J. D. Helvetica Chimica Acta, Vol. 52, Issue 7 https://doi.org/10.1002/hlca.19690520713	journal	January 1969
Probing the Dynamics of a Protein Hydrophobic Core by Deuteron Solid-State Nuclear Magnetic Resonance Spectroscopy Vugmeyster, Liliya; Ostrovsky, Dmitry; Ford, Joseph J. Journal of the American Chemical Society, Vol. 131, Issue 38 https://doi.org/10.1021/ja902977u	journal	September 2009
Amphidynamic Crystals of a Steroidal Bicyclo[2.2.2]octane Rotor: A High Symmetry Group That Rotates Faster than Smaller Methyl and Methoxy Groups Rodríguez-Molina, Braulio; Pérez-Estrada, Salvador; Garcia-Garibay, Miguel A. Journal of the American Chemical Society, Vol. 135, Issue 28 https://doi.org/10.1021/ja4024463	journal	May 2013
Dynamic Motion of Building Blocks in Porous Coordination Polymers Horike, Satoshi; Matsuda, Ryotaro; Tanaka, Daisuke Angewandte Chemie International Edition, Vol. 45, Issue 43 https://doi.org/10.1002/anie.200603196	journal	November 2006
Defect-Tolerant Aligned Dipoles within Two-Dimensional Plastic Lattices Thomas, John C.; Schwartz, Jeffrey J.; Hohman, J. Nathan ACS Nano, Vol. 9, Issue 5 https://doi.org/10.1021/acsnano.5b01329	journal	April 2015
Relaxation Effects in Nuclear Magnetic Resonance Absorption Bloembergen, N.; Purcell, E. M.; Pound, R. V. Physical Review, Vol. 73, Issue 7 https://doi.org/10.1103/PhysRev.73.679	journal	April 1948
Amphidynamic Character of Crystalline MOF-5: Rotational Dynamics of Terephthalate Phenylenes in a Free-Volume, Sterically Unhindered Environment Gould, Stephanie L.; Tranchemontagne, David; Yaghi, Omar M. Journal of the American Chemical Society, Vol. 130, Issue 11, p. 3246-3247 https://doi.org/10.1021/ja077122c	journal	March 2008
Design and synthesis of an exceptionally stable and highly porous metal-organic framework Li, Hailian; Eddaoudi, Mohamed; M., O'Keeffe Nature, Vol. 402, Issue 6759, p. 276-279 https://doi.org/10.1038/46248	journal	November 1999
Ultra-fast Rotors for Molecular Machines and Functional Materials via Halogen Bonding: Crystals of 1,4-Bis(iodoethynyl)bicyclo[2.2.2]octane with Distinct Gigahertz Rotation at Two Sites Lemouchi, Cyprien; Vogelsberg, Cortnie S.; Zorina, Leokadiya Journal of the American Chemical Society, Vol. 133, Issue 16 https://doi.org/10.1021/ja200503j	journal	April 2011
Artificial Molecular Rotors Kottas, Gregg S.; Clarke, Laura I.; Horinek, Dominik Chemical Reviews, Vol. 105, Issue 4 https://doi.org/10.1021/cr0300993	journal	April 2005
Applicability of the BET Method for Determining Surface Areas of Microporous Metal−Organic Frameworks Walton, Krista S.; Snurr, Randall Q. Journal of the American Chemical Society, Vol. 129, Issue 27 https://doi.org/10.1021/ja071174k	journal	July 2007
Deuterium magnetic resonance study of a smectic liquid crystal Luz, Z.; Hewitt, R. C.; Meiboom, S. The Journal of Chemical Physics, Vol. 61, Issue 5 https://doi.org/10.1063/1.1682172	journal	September 1974
Crystalline molecular machines: function, phase order, dimensionality, and composition Vogelsberg, Cortnie S.; Garcia-Garibay, Miguel A. Chem. Soc. Rev., Vol. 41, Issue 5 https://doi.org/10.1039/C1CS15197E	journal	January 2012

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A de novo strategy for predictive crystal engineering to tune excitonic coupling Haldar, Ritesh; Mazel, Antoine; Krstić, Marjan Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-10011-8	journal	May 2019
Anisotropic Thermal Expansion as the Source of Macroscopic and Molecular Scale Motion in Phosphorescent Amphidynamic Crystals Jin, Mingoo; Yamamoto, Sho; Seki, Tomohiro Angewandte Chemie International Edition, Vol. 58, Issue 50 https://doi.org/10.1002/anie.201909048	journal	October 2019
Libration of phenyl groups detected by VT-SSNMR: Comparison with X-ray crystallography Nieto, Carla I.; Cabildo, Pilar; García, M. Ángeles Magnetic Resonance in Chemistry, Vol. 56, Issue 11 https://doi.org/10.1002/mrc.4754	journal	June 2018
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Nanoscale rotational dynamics of four independent rotators confined in crowded crystalline layers Rodríguez-Fortea, Antonio; Canadell, Enric; Wzietek, Pawel Nanoscale, Vol. 12, Issue 15 https://doi.org/10.1039/d0nr00858c	journal	January 2020
Fast motion of molecular rotors in metal–organic framework struts at very low temperatures Perego, Jacopo; Bracco, Silvia; Negroni, Mattia Nature Chemistry https://doi.org/10.1038/s41557-020-0495-3	journal	July 2020
Synthesis of dipolar molecular rotors as linkers for metal-organic frameworks Hamer, Sebastian; Röhricht, Fynn; Jakoby, Marius Beilstein-Institut https://doi.org/10.5445/ir/1000096351	text	January 2019
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Synthesis of dipolar molecular rotors as linkers for metal-organic frameworks Hamer, Sebastian; Röhricht, Fynn; Jakoby, Marius Beilstein Journal of Organic Chemistry, Vol. 15 https://doi.org/10.3762/bjoc.15.132	journal	January 2019
Anisotropic Thermal Expansion as the Source of Macroscopic and Molecular Scale Motion in Phosphorescent Amphidynamic Crystals Jin, Mingoo; Yamamoto, Sho; Seki, Tomohiro Angewandte Chemie, Vol. 131, Issue 50 https://doi.org/10.1002/ange.201909048	journal	October 2019
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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
Environmental Molecular Sciences Laboratory
metal-organic frameworks
molecular rotors
molecular machines
smart materials
amphidynamic crystals